CN104797729B - Resistance to hydrogen embrittlement excellent steel wire for high-strength spring material and its manufacture method and high-strength spring - Google Patents
Resistance to hydrogen embrittlement excellent steel wire for high-strength spring material and its manufacture method and high-strength spring Download PDFInfo
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- CN104797729B CN104797729B CN201380060180.6A CN201380060180A CN104797729B CN 104797729 B CN104797729 B CN 104797729B CN 201380060180 A CN201380060180 A CN 201380060180A CN 104797729 B CN104797729 B CN 104797729B
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 108
- 239000001257 hydrogen Substances 0.000 title claims abstract description 108
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 96
- 239000010959 steel Substances 0.000 title claims abstract description 96
- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 229910000734 martensite Inorganic materials 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 12
- 238000005496 tempering Methods 0.000 claims description 43
- 238000010438 heat treatment Methods 0.000 claims description 38
- 238000010791 quenching Methods 0.000 claims description 38
- 230000000171 quenching effect Effects 0.000 claims description 33
- 230000014759 maintenance of location Effects 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000005452 bending Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 2
- 238000005275 alloying Methods 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 description 17
- 230000006866 deterioration Effects 0.000 description 17
- 230000000694 effects Effects 0.000 description 17
- 230000007812 deficiency Effects 0.000 description 14
- 229910001566 austenite Inorganic materials 0.000 description 11
- 238000005204 segregation Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000000717 retained effect Effects 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 229910017112 Fe—C Inorganic materials 0.000 description 3
- 229910000639 Spring steel Inorganic materials 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 229910000851 Alloy steel Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 229910001563 bainite Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 229910001567 cementite Inorganic materials 0.000 description 2
- 238000005262 decarbonization Methods 0.000 description 2
- 238000005261 decarburization Methods 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910001562 pearlite Inorganic materials 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 238000005491 wire drawing Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- -1 not being dissolved Inorganic materials 0.000 description 1
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/34—Methods of heating
- C21D1/42—Induction heating
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
- C21D1/18—Hardening; Quenching with or without subsequent tempering
- C21D1/19—Hardening; Quenching with or without subsequent tempering by interrupted quenching
- C21D1/22—Martempering
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/001—Heat treatment of ferrous alloys containing Ni
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/002—Heat treatment of ferrous alloys containing Cr
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/004—Heat treatment of ferrous alloys containing Cr and Ni
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/005—Heat treatment of ferrous alloys containing Mn
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D6/00—Heat treatment of ferrous alloys
- C21D6/008—Heat treatment of ferrous alloys containing Si
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/06—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires
- C21D8/065—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of rods or wires of ferrous alloys
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/02—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for springs
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/525—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length for wire, for rods
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/52—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
- C21D9/54—Furnaces for treating strips or wire
- C21D9/56—Continuous furnaces for strip or wire
- C21D9/60—Continuous furnaces for strip or wire with induction heating
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/08—Ferrous alloys, e.g. steel alloys containing nickel
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/42—Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16F—SPRINGS; SHOCK-ABSORBERS; MEANS FOR DAMPING VIBRATION
- F16F1/00—Springs
- F16F1/02—Springs made of steel or other material having low internal friction; Wound, torsion, leaf, cup, ring or the like springs, the material of the spring not being relevant
- F16F1/021—Springs made of steel or other material having low internal friction; Wound, torsion, leaf, cup, ring or the like springs, the material of the spring not being relevant characterised by their composition, e.g. comprising materials providing for particular spring properties
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D2211/00—Microstructure comprising significant phases
- C21D2211/008—Martensite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Abstract
The present invention provides a kind of steel wire for high-strength spring material, its be tempered martensite be more than 80 area %, the steel wire for high-strength spring material that tensile strength is more than 1900MPa, chemical composition as defined in satisfaction forms, and C and Si meets the relation of following (1) formulas, old austinite grain size number is more than No. 10, and hydrogen occlusion amount is more than 14.0ppm, thus, even if suppressing the addition of alloying element, resistance to hydrogen embrittlement also ensure that.Wherein, [C] and [Si] represents C and Si content (quality %) to 0.73%≤[C]+[Si]/8≤0.90%... (1) respectively.
Description
Technical field
The present invention relates to a kind of excellent steel wire for high-strength spring material of resistance to hydrogen embrittlement (hydrogen embrittlement resistance) and its manufacture
Method and high-strength spring.Specifically, it is related to a kind of steel wire material for spring and its manufacture method and high-strength spring,
The steel wire material for spring be as the helical spring used in the state of (Q-tempering) in modifier treatment material it is useful
Steel wire material for spring, even if tensile strength is more than 1900MPa high intensity, resistance to hydrogen embrittlement is also excellent.
Background technology
In order to the reduction of exhaust, fuel consumption rise and need lightweight, for automobile etc. helical spring (for example, with
Valve spring, bearing spring in engine, suspension etc. etc.) it is required high intensity.Because the spring of high intensity easily produces hydrogen
Fragility, therefore, for the steel wire material for spring of the manufacture for spring, it is desirable to which resistance to hydrogen embrittlement is excellent.
Method as the resistance to hydrogen embrittlement for improving steel wire for high-strength spring material, it is known that control chemical composition composition, tissue
Deng method.But alloying element largely is used in these methods, may not from the viewpoint of manufacturing cost, saving resource
It is preferable.
Further, as known to the manufacture method of spring：Hardening heat is heated to, after being thermoformed into spring shape, oil cooling is simultaneously
The method of tempering；With by after steel wire rod Q-tempering, method of the cold forming into spring shape.In addition, in the cold forming side of the latter
In method, it is also known that the Q-tempering before being formed with high-frequency heating, such as in patent document 1, it is known that carried out after cold-drawn high
Frequency heats, and Q-tempering carries out the technology of tissue adjustment.The technique improves delayed fracture characteristic, and its reason is as follows, leads to
Cross and the tissue point rate of pearlite is set to the tissue point rate of less than 30%, martensite or bainite is set to more than 70%, then with
Defined sectional shrinkage carries out cold-drawn, then carries out Q-tempering, thus reduces not melting for the starting point as delayed fracture
Carbide content.
In patent document 2, in embodiment, Wire Drawing and high-frequency heating are carried out to rolled stock, to carry out Q-tempering
Processing.The technology is to realize the technology for ensuring disc spring (coiling) property and the spring with high intensity and high tenacity.But should
Technology is conceived to disc spring, does not have any consideration for resistance to hydrogen embrittlement.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2004-143482 publications
Patent document 2：Japanese Unexamined Patent Publication 2006-183137 publications
The content of the invention
Invent problem to be solved
Completed currently invention addresses problem as described above, its object is to provide to be in manufacture tensile strength
During more than 1900MPa steel wire for high-strength spring material, even if suppressing the addition of alloying element, resistance to hydrogen embrittlement also ensure that
Steel wire for high-strength spring material and the manufacture method and high-strength spring for it.
For solving the method for problem
The steel wire material for spring of the invention that above-mentioned purpose can be reached is that tempered martensite is more than 80 area %, tension
Intensity is more than 1900MPa steel wire for high-strength spring material, and it is characterized by,
The steel wire rod contains respectively：
C：0.50~0.70% (representing quality %, following same on chemical composition composition),
Si：1.50~2.3%,
Mn：0.3~1.5%,
P：Less than 0.015% (not including 0%),
S：Less than 0.015% (not including 0%) and
Al：0.001~0.10%, and C and Si meet the relation of following (1) formulas, surplus is iron and inevitable impurity,
Old austinite grain size number is more than No. 10, and hydrogen occlusion amount is more than 14.0ppm.
0.73%≤[C]+[Si]/8≤0.90% ... (1)
Wherein, [C] and [Si] represents C and Si content (quality %) respectively.
The steel wire material for spring of the present invention can as needed also containing belong to a kind of any one of following (a)~(f) with
On element.
(a)Cu：Less than 0.7% (not including 0%) and Ni：It is at least one kind of in less than 0.7% (not including 0%)
(b)Ti：Not less than 0.10% (not including 0%)
(c)B：Not less than 0.010% (not including 0%)
(d)Nb：Less than 0.10% (not including 0%) and Mo：It is at least one kind of in less than 0.5% (not including 0%)
(e)V：Not less than 0.4% (not including 0%)
(f)Cr：Not less than 0.8% (not including 0%)
The steel wire material for spring of the present invention turns into a diameter of 7~20mm or so steel wire rod.
On the other hand, the manufacture method that can reach the steel wire material for spring of the invention of above-mentioned purpose is characterised by,
The steel formed using chemical composition as described above is met, are quenched and are tempered in the way of following full terms are met
Handle to manufacture.
(quenching condition)
Quenching temperature T1：850~1000 DEG C
From 100 DEG C of average heating speed HR1 untill quenching temperature T1：More than 40 DEG C/sec
In quenching temperature T1 retention time t1：Less than 90 seconds
Average cooling rate CR1 after Quench heating from 300 DEG C to 80 DEG C：More than 5 DEG C/sec and less than 100 DEG C/sec
(tempered condition)
Tempering heating-up temperature T2：350~550 DEG C
From 100 DEG C of average heating speed HR2 untill tempering heating-up temperature T2：More than 30 DEG C/sec
In tempering heating-up temperature T2 retention time t2：Less than 90 seconds
Average cooling rate CR2 after tempering heating untill tempering heating-up temperature T2 to 100 DEG C：More than 30 DEG C/sec
The present invention includes the high-strength spring using high-strength spring steel wire forming as described above, even in such
Resistance to hydrogen embrittlement is also excellent in high-strength spring.
Invention effect
According to the present invention, even if not adding alloying element largely, can also obtain showing that tensile strength is more than 1900MPa
High intensity and the excellent steel wire material for spring of resistance to hydrogen embrittlement.Such steel wire material for spring can suppress steel product cost and
Resistance to hydrogen embrittlement is excellent.As a result, automobile (such as can be used as using the spring for the high intensity for supplying extremely difficult generation hydrogen embrittlement at a low price
The helical springs such as the pendulum spring with one of part).
Embodiment
The present inventor etc. are directed to the condition of Q-tempering etc. to influence caused by the characteristic of steel wire rod, are carried out from various angles
Research.As a result, find that low-alloy steel is made by C, Si amount using low price suitable control as essential element, and
Short time heating is carried out by high-frequency heating, is thus significantly increased hydrogen trapping position, resistance to hydrogen embrittlement greatly improves, so as to complete
The present invention.Hereinafter, each important document specified in the present invention is illustrated.
(tempered martensite：More than 80 area %)
The present invention steel wire rod be tissue based on tempered martensite (with all organize in proportion be calculated as 80 faces
Product more than %) steel wire rod.In order to ensure the high intensity in steel wire rod and high tenacity, it is necessary to by carrying out Q-tempering processing,
Form the tissue of tempered martensite phosphor bodies.Tempered martensite is preferably more than 90 area % (more preferably 100 area %).As return
Tissue beyond fiery martensite, bainite, ferrite, pearlite etc. can be included, even if comprising these also for 10 area % with
Under.Preferably below 5 area % (more preferably 0 area %).
(old austinite grain size number is more than No. 10)
In order to ensure good resistance to hydrogen embrittlement, the granular of old austenite crystal is effectively realized.From such viewpoint
Set out, it is necessary to make old austinite grain size number be more than No. 10.Preferably more than No. 11, more preferably more than No. 12.Need
Illustrate, in order that old austinite grain size number is more than No. 10, Q-tempering effectively carried out by high-frequency heating,
In common stove heat, firing rate, the heat time is elongated and the crystal grain-growth under high-temperature heating is notable, and the thick of crystal grain occurs
Change, it is thus impossible to realize the granular of old austenite crystal.
(hydrogen occlusion amount：More than 14.0ppm)
For the steel wire rod of the present invention, chemical composition composition is also required to suitably set (aftermentioned), in steel wire rod
Hydrogen occlusion amount is also required to suitably set.The hydrogen occlusion amount represents to allow hydrogen amount, the more how resistance to hydrogen embrittlement of hydrogen occlusion amount in steel wire rod
Property becomes better.From such a viewpoint, it is necessary to make hydrogen occlusion amount be more than 14.0ppm.Preferably more than 14.5ppm,
More preferably more than 15.0ppm., can so as to which resistance to hydrogen embrittlement becomes the reasons why good for by suitably setting hydrogen occlusion amount
To think it is probably that hydrogen occlusion amount in this experiment represents the hydrogen amount trapped by trickle carbide, by increasing by trickle carbide
The hydrogen amount of trapping, hydrogen intrusion, accumulation to crystal boundary can be suppressed, the resistant to hydrogen rupture ruptured by intercrystalline failure can be realized
The improvement of (resistance to hydrogen embrittlement).It should be noted that if hydrogen occlusion amount is more, accelerated to the intrusion speed of the hydrogen of steel, thus from
From the viewpoint of the intrusion for suppressing superfluous hydrogen, hydrogen occlusion amount is preferably below 25ppm, more preferably below 20ppm.
In order to increase hydrogen occlusion amount, make carbide (for the carbide in the steel carbide of Fe-C systems of Fe-C systems
It is overriding) it is finely dispersed in steel and becomes important.In order that Fe-C systems carbide (hereinafter simply referred to as " carbide ") is trickle
It is scattered that, it is necessary to suppress the generation of the thick carbide in steel, (1200 DEG C of soaking (soaking) based on aftermentioned embodiment also have
Relation), the Si's that the C as the essential element of carbide (except Fe) and the size to the carbide of precipitation are impacted
Amount is set to appropriate scope, increases the amount of carbide, and generate trickle carbide.In addition, it is necessary in appropriate scope
Q-tempering (aftermentioned) is controlled, suppresses the generation of carbide not being dissolved, generates trickle carbide.
The present invention steel wire material for spring be the content that suppressed to alloying element low-alloy steel, its chemical composition
The scope restriction reason of each composition (element) in composition is as follows.
(C：0.50~0.70%)
C is for ensuring that element necessary to the high intensity of steel wire material for spring, and turns into hydrogen trap portion to generate
The trickle carbide of position is also necessary.From such a viewpoint, it is necessary to contain more than 0.50% C.C content it is preferred under
It is limited to more than 0.54% (more preferably more than 0.58%).But if C content becomes superfluous, it is also easily raw after Q-tempering
Into thick retained austenite, the carbide not being dissolved, resistance to hydrogen embrittlement reduces on the contrary sometimes.In addition, C is also to deteriorate corrosion resistance
Element, therefore need to suppress to improve as the saprophage fatigue properties of the spring product (pendulum spring etc.) of end article
C content.From such a viewpoint, C content is needed for less than 0.70%.The preferred upper limit of C content is less than 0.65% (more excellent
Select less than 0.62%).
(Si：1.50~2.3%)
Si is for ensuring that element necessary to intensity, and with making the trickle effect of carbide.In order to effectively send out
Wave such effect, it is necessary to contain more than 1.50% Si.The preferred lower limit of Si contents be more than 1.7% (more preferably 1.9% with
On).On the other hand, Si is also the element for promoting decarburization, if therefore Si contain superfluously, the decarburized layer of steel surface formation quilt
Promote, need to peel off process to eliminate decarburized layer, cause the increase of manufacturing cost.In addition, non-solid solution carbides also become more,
Resistance to hydrogen embrittlement reduces.From such a viewpoint, the upper limit of Si contents is set to less than 2.3% in the present invention.Si contents
Preferred upper limit is less than 2.2% (more preferably less than 2.1%).
(0.73%≤[C]+[Si]/8≤0.90%：The relation of above-mentioned (1) formula)
(in [C]+[Si]/8) are the carbide for turning into hydrogen trapping position in more than 0.73% and less than 0.90% scope
Trickle and separate out in large quantities, resistance to hydrogen embrittlement improves.If the value of ([C]+[Si]/8) is less than 0.73%, as hydrogen trapping position
The amount of trickle carbide is reduced, hydrogen embrittlement deterioration.On the other hand, the value of (if [C]+[Si]/8) is more than 0.90%, holds
The carbide for easily generate thick retained austenite, not being dissolved, hydrogen embrittlement deterioration.The preferred lower limit of ([C]+[Si]/8) is
More than 0.75% (more preferably more than 0.78%, further preferred more than 0.81%), preferred upper limit is less than 0.89% (more preferably
Less than 0.87%).
(Mn：0.3~1.5%)
Mn is utilized as deoxidant element, and forms MnS with being reacted as the S of the harmful element in steel, is to S
Innoxious beneficial element.In addition, Mn also contributes to the element of intensity raising.In order to effectively play these effects, it is necessary to
Contain more than 0.3% Mn.The preferred lower limit of Mn contents is more than 0.5% (more preferably more than 0.7%).But if Mn contents
Become superfluous, then hardenability increases, and toughness reduces and hydrogen embrittlement deterioration.From such a viewpoint, it is necessary to make the Mn contents be
Less than 1.5%.The preferred upper limit of Mn contents is less than 1.3% (more preferably less than 1.1%).
(P：Not less than 0.015% (not including 0%))
P is the harmful element for deteriorating the ductility (disc spring) of steel wire rod, it is therefore desirable for as far as possible few.In addition, P is easily in crystalline substance
Boundary is segregated, and causes embrittlement of grain boundaries, crystal boundary is more easily damaged due to hydrogen, and resistance to hydrogen embrittlement is had undesirable effect.From such sight
Point is set out, and its upper limit is set into less than 0.015%.The preferred upper limit of P content be less than 0.010% (more preferably 0.008% with
Under).
(S：Not less than 0.015% (not including 0%))
S and above-mentioned P also makes the harmful element that the ductility (disc spring) of steel wire rod deteriorates, it is therefore desirable for as far as possible few.
In addition, S causes embrittlement of grain boundaries easily in cyrystal boundary segregation, crystal boundary is more easily damaged due to hydrogen, and bad shadow is caused to resistance to hydrogen embrittlement
Ring.From such a viewpoint, its upper limit is set to less than 0.015%.The preferred upper limit of S contents is less than 0.010% (more excellent
Select less than 0.008%).
(Al：0.001~0.10%)
Al adds mainly as deoxidant element.In addition, Al and N reaction and forming A1N makes solid solution N innoxious, and also have
Help the granular of tissue.In order to give full play to these effects, it is necessary to which Al content is set into more than 0.001%.Preferably
More than 0.002%.But Al and Si also promotes the element of decarburization, therefore largely the spring steel wire containing Si needs to press down
Al amounts processed, the upper limit of Al content is set to less than 0.10% in the present invention.Preferably less than 0.07%, more preferably 0.030%
Hereinafter, particularly preferably less than 0.020%.
The chemical composition of steel of the present invention is formed as described above, surplus includes iron and inevitable impurity.The present invention's
Even if steel wire material for spring substantially suppresses the alloying elements such as Cu, high intensity and excellent can also be reached by being formed with above-mentioned chemical composition
Different disc spring and resistance to hydrogen embrittlement, but following members for the purpose of possessing corrosion resistance etc., and can further be contained according to purposes
Element.The preferred scope setting reason of these elements is as described below.
(Cu：Less than 0.7% (not including 0%) and Ni：It is at least one kind of in 0.7% (not including 0%))
Cu is suppression to superficial decarbonization, corrosion proof improves effective element.But if Cu is included superfluously, heat
It can be ruptured during processing, or cost increase.Therefore, in the present invention, the upper limit of Cu contents is preferably set to less than 0.7%.More
Preferably less than 0.5%, more preferably less than 0.3% (being even more preferably less than 0.18%).It should be noted that
In order to play such effect, more than 0.05% Cu, more preferably more than 0.10% are preferably comprised.
It is suppression to superficial decarbonization that Ni is same with Cu, corrosion proof improves effective element.But if Ni is wrapped superfluously
Contain, then cost increase.Therefore, the upper limit of Ni contents is preferably set to less than 0.7% in the present invention.More preferably less than 0.5%,
More preferably less than 0.3% (being even more preferably less than 0.18%).It should be noted that in order to play such effect
Fruit, preferably comprise more than 0.05% Ni, more preferably more than 0.10%.
(Ti：Not less than 0.10% (not including 0%))
Ti is to react to form sulfide and to realizing S innoxious useful element with S.In addition, Ti, which also has, forms carbon
Nitride and will organize granular effect.But if Ti contents become superfluous, thick Ti sulfide is formed sometimes and is prolonged
Property deterioration.Therefore, in the present invention, the preferred upper limit of Ti contents is set to less than 0.10%.From the viewpoint of cost reduction, more
It is preferred that suppress below 0.07%.It should be noted that in order to play above-mentioned effect, more than 0.02% Ti is preferably comprised,
More preferably more than 0.05%.
(B：Not less than 0.010% (not including 0%))
B is that hardenability improves element, or with strengthening the effect of old austenite grain boundary, contribute to the member of suppression destroyed
Element.But even if superfluous contain B the effect above also saturation, therefore the upper limit of B content is preferably set to less than 0.010%.It is more excellent
Elect less than 0.0050% as.It should be noted that in order to effectively play above-mentioned effect, B content is preferably set to 0.0005%
More than, more preferably more than 0.0010%.
(Nb：Less than 0.10% (not including 0%) and Mo：It is at least one kind of in less than 0.5% (not including 0%))
Nb forms carbonitride with C, N, is essentially to facilitate the element of tissue granular.But if Nb contents became
It is surplus, then form the deteriorated ductility of thick carbonitride and steel.It is therefore preferable that the upper limit of Nb contents is set to less than 0.10%.
From the viewpoint of cost reduction, more preferably suppress below 0.07%.It should be noted that in order to effectively play it is above-mentioned that
The effect of sample, Nb contents are preferably set to more than 0.003%, more preferably more than 0.005%.
Mo is also with Nb again it is forming carbonitride with C, N and contributing to the element of tissue granular.Mo is still to tempering
Intensity afterwards ensures also effective element.But if Mo contents become superfluous, form the ductility of thick carbonitride and steel
(disc spring) deteriorates.It is therefore preferable that the upper limit of Mo contents is set to less than 0.5%, more preferably less than 0.4%.Need to illustrate
, in order to effectively play above-mentioned effect, Mo contents are preferably set to more than 0.15%, more preferably more than 0.20%.
(V：Not less than 0.4% (not including 0%))
V contributes to intensity to improve, crystal grain granular.But if V content becomes superfluous, cost increase.Therefore, V contains
The upper limit of amount is preferably set to less than 0.4%, more preferably less than 0.3%.It is it should be noted that above-mentioned in order to effectively play
Effect, V content are preferably set to more than 0.1%, more preferably more than 0.15%.
(Cr：Not less than 0.8% (not including 0%))
Cr is to improve effective element to corrosion proof.But Cr is carbide generation tendency is strong, it is only to be formed in steel
From carbide and the element that is easily fused into cementite with high concentration.It is effective containing a small amount of Cr, but in high frequency
In heating, heat time of quenching process is the short time, therefore the austenitizing for making carbide, cementite etc. fuse into mother metal
Easily become insufficient.Therefore, if largely containing Cr, occur to be dissolved the carburizing of Cr systems carbide, metal Cr in high concentration
The melting residual of body, and turn into stress raiser, therefore be easily destroyed, resistance to hydrogen embrittlement reduces.From such a viewpoint, contain
Upper limit during Cr is preferably set to less than 0.8%.More preferably less than 0.5% (further preferred less than 0.4%).Need what is illustrated
It is that, in order to effectively play above-mentioned effect, Cr contents are preferably set to more than 0.01%, more preferably more than 0.05%.
Then, the method for the steel wire material for spring for manufacturing the present invention is illustrated.The spring steel line of the present invention
Material can be for example rolled after obtaining steel wire rod after steel are founded, implements cold-drawn wire processing as needed and (steel is made
Line), then carry out high-frequency quenching temper and obtain.Ensure high intensity, while can improve to be readily formed
The above-mentioned tissue of resistance to hydrogen embrittlement by following main points, it is necessary to carry out Q-tempering processing.It should be noted that following heat treatment bar
Part is the value in steel surface measure.
(quenching condition)
If quenching temperature T1 becomes to be above 1000 DEG C, old austenite crystal coarsening, characteristic (resistance to hydrogen embrittlement) drops
It is low.In addition, if quenching temperature T1 is too high, the amount of coarse grains and crystal boundary is reduced, it is impossible to obtains trickle carbide
(from crystal boundary preferentially carbide precipitate, therefore carbide easily disperses when crystal boundary is more).Therefore quenching temperature T1 is set to
Less than 1000 DEG C.Temperature T1 is preferably less than 980 DEG C, more preferably less than 930 DEG C.On the other hand, if quenching temperature
T1 gets lower than 850 DEG C, then carbide is deficiently dissolved, it is impossible to austenitizing is fully realized, in the Q-tempering process,
Tempered martensite can not be substantially ensured that, it is impossible to obtain high intensity.In addition, if quenching temperature T1 is too low, carbide
Deficiently it is dissolved, the carbide residual not being dissolved, carbide content deficiency.Quenching temperature T1 is preferably more than 870 DEG C, more
Preferably more than 900 DEG C.
If slower than 40 DEG C/sec from 100 DEG C of average heating speed HR1 untill quenching temperature T1, old Ovshinsky
Body coarse grains, characteristic reduce.In addition, if average heating speed HR1 is excessively slow, the amount of coarse grains and crystal boundary is reduced,
Trickle carbide can not be obtained.Therefore, average heating speed HR1 is more than 40 DEG C/sec.It is preferably more than 50 DEG C/sec, more excellent
Elect more than 100 DEG C/sec as.On the other hand, from the viewpoint of temperature control, the above-mentioned average heating speed HR1 upper limit is 400
DEG C/sec or so.It should be noted that for not specially required from room temperature to 100 DEG C of average heating speed.
If being longer than 90 seconds in quenching temperature T1 retention time t1, old austenite crystal coarsening, characteristic (resistant to hydrogen
Fragility) reduce.In addition, if retention time t1 is long, the amount of coarse grains and crystal boundary is reduced, it is impossible to obtains trickle carbonization
Thing.Therefore, retention time t1 must be set to less than 90 seconds.Retention time t1 is preferably less than 60 seconds, more preferably less than 40 seconds.
It should be noted that in order to prevent carbide fuse into deficiency caused by austenitizing deficiency, and obtain desired tissue
(tissues of tempered martensite phosphor bodies), preferably the t1 is set to more than 5 seconds.In addition, if retention time t1 is too short, carbide is not
Fully it is dissolved, the carbide residual not being dissolved, carbide content deficiency.More preferably more than 10 seconds, more preferably 15 seconds
More than.
Average cooling rate (CR1) after Quench heating from 300 DEG C to 80 DEG C is if excessively slow, and quenching becomes insufficient, no
It can ensure that intensity.Therefore, average cooling rate CR1 must be set to more than 5 DEG C/sec.Average cooling rate CR1 is preferably 10 DEG C/
More than second, more preferably more than 20 DEG C/sec.It should be noted that the average cooling rate CR1 upper limit is 100 DEG C/sec or so.
(tempered condition)
If tempering heating-up temperature T2 is too low, under tempering, intensity becomes too high, and producing tube reducing value terrifically reduces this
The problem of sample.On the other hand, if tempering heating-up temperature T2 is uprised, it is difficult to reach tensile strength：More than 1900MPa is (preferably
More than 2000MPa).Tempering heating-up temperature T2 scope is 350~550 DEG C of scope (preferably 400~500 DEG C), can basis
Desired strength suitably determines.
If slow from 100 DEG C of average heating speed HR2 untill tempering heating-up temperature T2, carbide coarsening, it is impossible to
Ensure desired characteristic.In addition, if average heating speed HR2 is excessively slow, the generation frequency of the carbide from crystal boundary reduces, no
Trickle carbide can be obtained.Therefore, in the present invention, average heating speed HR2 is set to more than 30 DEG C/sec.Preferably 40 DEG C/
More than second, more preferably more than 50 DEG C/sec.But if average heating speed HR2 is too fast, temperature control difficult, easily
Produce the deviation in intensity, therefore preferably less than 300 DEG C/sec, more preferably less than 200 DEG C/sec.It is it should be noted that right
Do not specially required in from room temperature to 100 DEG C of average heating speed.
If being longer than 90 seconds in tempering heating-up temperature T2 retention time t2, carbide coarsening, resistance to hydrogen embrittlement reduces.Protect
It is preferably less than 70 seconds to hold time t2, more preferably less than 50 seconds, more preferably less than 40 seconds, particularly preferably 12 seconds with
Under.On the other hand, the present invention is premised on carrying out high-frequency heating, if retention time t2 is too short, in the situation of particle size steel wire rod
Under, easily produce the hardness deviation in the section of circumferencial direction, it is difficult to realize that stable intensity improves.Therefore, in the present invention,
It is preferred that retention time t2 is set to more than 5 seconds.Retention time t2 is more preferably more than 7 seconds, more preferably more than 10 seconds.
It should be noted that intensity as requested suitably adjusts retention time t2 now within the above range.
If from tempering heating-up temperature T2 (being 400 DEG C when wherein, above-mentioned T2 is more than 400 DEG C) to 100 DEG C after tempering heating
Average cooling rate CR2 it is slow, then carbide coarsening and cannot ensure the (life of the carbide from crystal boundary of desired characteristic
Reduced into frequency, it is impossible to obtain trickle carbide).Therefore, in the present invention, above-mentioned average cooling rate CR2 is set to 30
More than DEG C/sec.Preferably more than 40 DEG C/sec, more preferably more than 50 DEG C/sec.It should be noted that average cooling rate CR2
The upper limit be 300 DEG C/sec or so.In addition, for being not particularly limited from 100 DEG C to the average cooling rate of room temperature.
A diameter of such as 7~20mm (preferably 10~15mm) of the steel wire material for spring of the present invention.The steel wire material for spring
Then shaped by spring as high-strength spring, it is excellent and play good mechanical property that resistance to hydrogen embrittlement can be obtained
High-strength spring.
In order to obtain excellent resistance to hydrogen embrittlement, the segregation for the steel founded is reduced, even improving C, Si composition system
It is also required to reduce non-solid solution carbides, thick retained austenite.In addition, it is necessary to reduce segregation, the composition in steel is set to become equal
It is even, in tempered martensite, suppress the segregation of the carbide of generation, carbide is more finely dispersed in steel, increase quilt
The hydrogen amount of trickle carbide trapping.Therefore, the soaking for implementing to be heated more than 1200 DEG C after founding becomes important.In addition,
In rolling, become after also there is below the 30mm of reducing effect of segregation at low temperature, turn into 900 according to wire temperature (line temperature)
Mode more than DEG C, which adjusts rolling temperature, becomes important.
The application is based in Japanese patent application 2012-279437 CLAIM OF PRIORITYs filed in 21 days December in 2012
Interests.The full content of the specification of Japanese patent application filed in 21 days December in 2012 the 2012-279437th is at this
It is used to reference in application be cited.
【Embodiment】
Hereinafter, the present invention is further illustrated for embodiment, but the present invention is not limited by following embodiments certainly, certainly
Change can be applied in the range of it can be adapted to the forward and backward purport stated to implement, these are both contained in the technology model of the present invention
Enclose.
Table 1 below, the steel (steel No.1~63) of the composition of chemical composition shown in 2 are founded in small size vacuum calciner,
After being forged into the steel billet of 155mm square (cross sectional shape is 155mm × 155mm), implement the soaking of 1 hour at 1200 DEG C.Pass through
Implement soaking, segregation is reduced, and non-solid solution carbides, thick retained austenite can be also reduced even improving C, Si composition system
Body, excellent resistance to hydrogen embrittlement can be obtained.In addition, by the reduction of segregation, the composition in steel becomes uniform, in tempered martensite
In tissue, the skewness of the carbide of generation disappears, and it can be made more to be finely dispersed in steel, by increasing capacitance it is possible to increase by trickle carbonization
The hydrogen amount of thing trapping.After soaking, hot rolling and the wire rod for obtaining diameter 14.3mm.In rolling, reaching below 30mm line footpath
In the stage, rolling temperature is adjusted in the way of line temperature turns into more than 900 DEG C.Then, by wire rod cold-drawn processing (wire drawing) to directly
Footpath 12.0mm and after steel wire is made, in high-frequency induction heating furnace, Q-tempering is carried out under conditions of following, obtains spring use
Steel wire.
(quenching condition for utilizing high frequency)
Quenching temperature T1：930℃
From 100 DEG C of average heating speeds untill quenching temperature T1：200 DEG C/sec
In quenching temperature T1 retention time t1：15 seconds
Average cooling rate CR1 after Quench heating from 300 DEG C to 80 DEG C：80 DEG C/sec
(tempered condition for utilizing high frequency)
According in tempering heating-up temperature T2：Set in the range of 350~550 DEG C as 2000MPa mode
From 100 DEG C of average heating speed HR2 untill tempering heating-up temperature T2：100 DEG C/sec
In tempering heating-up temperature T2 retention time t2：10 seconds
Average cooling rate CR2 after tempering heating untill heating-up temperature T2 to 100 DEG C：100 DEG C/sec
(quenching condition for utilizing stove heat)
Quenching temperature T1：900℃
From 100 DEG C of average heating speeds untill quenching temperature T1：2 DEG C/sec
In the retention time t1 of quenching temperature：10 minutes
Quench cooling velocity：80 DEG C/sec
(tempered condition for utilizing stove heat)
According in tempering heating-up temperature T2：Set in the range of 300~500 DEG C as 2000MPa mode
From 100 DEG C of average heating speeds untill tempering heating-up temperature T2：2 DEG C/sec
In tempering heating-up temperature T2 retention time t2：60 minutes
Average cooling rate after tempering heating untill heating-up temperature T2 to 100 DEG C：100 DEG C/sec
【Table 1】
【Table 2】
Using obtained steel wire, the evaluation (survey of old austinite grain size number of structure of steel is carried out using following method
Fixed, tempered martensite divides the measure of rate), the evaluation (measure of tensile strength) of tensile characteristics, resistance to hydrogen embrittlement, the hydrogen amount in steel
Evaluation.
(measure of old austinite grain size number)
Cross section D/4 positions by steel wire gather sample in the way of turning into sightingpiston, and the sample of the collection is embedded into tree
Fat, there is old austenite grain boundary using the corrosive liquid of picric acid system after grinding, utilize JIS G 0551：Method as defined in 2005
Obtain old austinite grain size number.Now confirmed using light microscope with 400 times, confirm the tissue of any one
In, relative to whole tissues, tempered martensite is more than 80 area %.
(evaluations (evaluation of disc spring) of tensile characteristics)
JIS14 test films are processed into, according to JIS Z 2241：1998, using universal testing machine in crosshead speed：
Tensile test, measure tensile strength TS are carried out under conditions of 10mm/ minutes.Then, it is that more than 1900MPa is commented by tensile strength TS
Valency is high intensity (qualified).
(evaluation (hydrogen embrittlement experiment) of resistance to hydrogen embrittlement)
Width is cut out from steel wire：10mm × thickness：1.5mm × length：65mm test film.Then, for test film
In the state of acting on 1400MPa stress by 4 points of bendings, it is 0.5mol, thiocyanic acid that test film is impregnated in into sulfuric acid in 1L
Potassium is in 0.01mol mixed solution.Apply-the 700mV's lower than SCE electrode (saturated calomel electrode) using potentiostat
Voltage, determine until rupturing the time (rupture time) untill occurring.Moreover, rupture time be more than 1100 seconds when be evaluated as it is resistance to
Hydrogen brittleness is excellent (judgement "○").
(measure of the hydrogen occlusion amount in steel wire)
Width is cut out from steel wire：10mm × thickness：1.0mm × length：30mm test film.Then, by test film in nothing
In the state of stress, it is impregnated in the mixed solution that sulfuric acid in 1L is 0.5mol, potassium rhodanide is 0.01mol.Using permanent electricity
In the state of position instrument applies the -700mV lower than SCE electrode voltage, kept for 15 hours, implement to release hydrogen amount immediately after taking-up
Measure.Hydrogen amount is released to be measured by the analysis that heats up using gas phase chromatographic device.Programming rate is with 100 DEG C/h of progress
Measure, using the releasing hydrogen amount untill 300 DEG C as hydrogen occlusion amount.When the hydrogen occlusion amount is more than 14.0ppm, hydrogen amount is determined as
“○”。
Its result is shown in Table 3 below, 4 together with heat treatment condition.
【Table 3】
【Table 4】
Thus result can be analyzed as follows.Understanding steel No.5~18,27,31~42,57~63 is met in the present invention
The embodiment of defined important document, play good resistance to hydrogen embrittlement.
On the other hand, steel No.1~4,19~26,28~30,43~56 are to be unsatisfactory for any specified in the present invention want
The comparative example of part, hydrogen embrittlement deterioration.That is, steel No.1~3 are that the value of [C]+[Si]/8 is unsatisfactory for model specified in the present invention
The example enclosed (C content is also insufficient, and it is also "×" that hydrogen amount, which judges), it is contemplated that bad to the number deficiency of trickle carbide, resistance to hydrogen embrittlement
Change.In addition, steel No.4 is the example (hydrogen amount judge also be "×") of C content deficiency, it is contemplated that to trickle carbide number not
Foot, hydrogen embrittlement deterioration.
Steel No.19 is that the value of ([C]+[Si]/8) exceedes the example of scope specified in the present invention, it is contemplated that to during quenching
Carbide fuses into deficiency, and hydrogen amount is determined as "○", but hydrogen embrittlement deterioration.Steel No.20,21 are the superfluous examples of C content
(value of ([C]+[Si]/8) is also above scope specified in the present invention), it is contemplated that fuse into deficiency, hydrogen amount to carbide during quenching
It is determined as "○", but hydrogen embrittlement deterioration.
Steel No.22 is that (value of ([C]+[Si]/8) is also above model specified in the present invention for the superfluous example of Si contents
Enclose), it is contemplated that deficiency is fused into carbide during quenching, hydrogen amount is determined as "○", but hydrogen embrittlement deterioration.Steel No.23 is
The value of ([C]+[Si]/8) is unsatisfactory for the example of scope specified in the present invention (it is also "×" that hydrogen amount, which judges), it is contemplated that to trickle carbon
The number deficiency of compound, hydrogen embrittlement deterioration.
Steel No.24 is that (value of ([C]+[Si]/8) is also unsatisfactory for model specified in the present invention to the insufficient example of Si contents
Enclose, it is also "×" that hydrogen amount, which judges), it is contemplated that to the number deficiency of trickle carbide, hydrogen embrittlement deterioration.Steel No.25 is that Si contains
Measure superfluous example, it is contemplated that fuse into deficiency to carbide during quenching, hydrogen amount is determined as "○", but hydrogen embrittlement deterioration.
Steel No.26 is the example of Si contents deficiency (it is also "×" that hydrogen amount, which judges), it is contemplated that to the number of trickle carbide
Deficiency, hydrogen embrittlement deterioration.Steel No.28 is the superfluous example of Mn contents, and hydrogen amount is determined as "○", but hydrogen embrittlement deterioration.
Steel No.29 is the superfluous example of P content, it is contemplated that to P in cyrystal boundary segregation and embrittlement of grain boundaries, hydrogen amount are determined as
"○", but hydrogen embrittlement deterioration.Steel No.30 is the superfluous example of S contents, it is contemplated that in cyrystal boundary segregation and embrittlement of grain boundaries, hydrogen amount
It is determined as "○", but hydrogen embrittlement deterioration.
Steel No.43~56 are the examples for carrying out stove heat, the grain size number number of old austenite it is small (coarsening,
And it is also "×" that hydrogen amount, which judges), hydrogen embrittlement deterioration.
Industrial applicability
The steel wire for high-strength spring material of the present invention is that tempered martensite is more than 80 area %, tensile strength is
More than 1900MPa steel wire for high-strength spring material, chemical composition as defined in satisfaction form, and C and Si meets following (1) formulas
Relation, old austinite grain size number is more than No. 10, and hydrogen occlusion amount is more than 14.0ppm, thus, even if suppressing alloy
The addition of element, also ensures that resistance to hydrogen embrittlement.
0.73%≤[C]+[Si]/8≤0.90% ... (1)
Wherein, [C] and [Si] represents C and Si content (quality %) respectively.
Claims (5)
1. a kind of steel wire for high-strength spring material, it is characterised in that it is that tempered martensite is more than 80 area %, tensile strength
For more than 1900MPa steel wire for high-strength spring material,
The steel wire rod is contained in terms of quality % respectively：
C：0.50~0.70%,
Si：1.50~2.3%,
Mn：0.3~1.5%,
P：Less than 0.015% and not include 0%,
S：Less than 0.015% and not include 0% and
Al：0.001~0.10%,
And C and Si meets the relation of following (1) formulas, surplus is iron and inevitable impurity, and old austinite grain size number is
More than No. 10, and hydrogen occlusion amount is more than 14.0ppm, also, acting on the shape of 1400MPa stress by 4 points of bendings
Under state, it is impregnated in the mixed solution that sulfuric acid in 1L is 0.5mol, potassium rhodanide is 0.01mol, applies ratio using potentiostat
Lower-the 700mV of SCE electrodes voltage, determining when rupturing the time untill occurring, rupture time is more than 1100 seconds,
0.73%≤[C]+[Si]/8≤0.89% ... (1)
Wherein, [C] and [Si] represents C and Si mass percentage content respectively.
2. steel wire for high-strength spring material as claimed in claim 1, it is also contained in terms of quality % and belongs to following (a)~(f)
Any one of more than a kind of element,
(a)Cu：Less than 0.7% and do not include 0% and Ni：Less than 0.7% and not include 0% in it is at least one kind of；
(b)Ti：Less than 0.10% and not include 0%；
(c)B：Less than 0.010% and not include 0%；
(d)Nb：Less than 0.10% and do not include 0% and Mo：Less than 0.5% and not include 0% in it is at least one kind of；
(e)V：Less than 0.4% and not include 0%；
(f)Cr：Less than 0.8% and not include 0%.
3. steel wire for high-strength spring material as claimed in claim 1 or 2, its a diameter of 7~20mm.
4. the manufacture method of the excellent steel wire for high-strength spring material of a kind of resistance to hydrogen embrittlement, it is characterised in that under the following conditions
High-frequency quenching and tempering are carried out to the wire rod or steel wire for meeting the chemical composition composition described in claim 1 or 2,
Quenching condition
Quenching temperature T1：850~1000 DEG C
From 100 DEG C of average heating speed HR1 untill quenching temperature T1：More than 40 DEG C/sec
In quenching temperature T1 retention time t1：Less than 90 seconds
Average cooling rate CR1 after Quench heating from 300 DEG C to 80 DEG C：More than 5 DEG C/sec and less than 100 DEG C/sec
Tempered condition
Tempering heating-up temperature T2：350~550 DEG C
From 100 DEG C of average heating speed HR2 untill tempering heating-up temperature T2：More than 30 DEG C/sec
In tempering heating-up temperature T2 retention time t2：Less than 90 seconds
Average cooling rate CR2 after tempering heating untill tempering heating-up temperature T2 to 100 DEG C：More than 30 DEG C/sec.
5. a kind of high-strength spring, obtained from it is the steel wire for high-strength spring material described in usage right requirement 1 or 2.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012279437A JP5973903B2 (en) | 2012-12-21 | 2012-12-21 | High strength spring steel wire excellent in hydrogen embrittlement resistance, method for producing the same, and high strength spring |
| JP2012-279437 | 2012-12-21 | ||
| PCT/JP2013/082380 WO2014097872A1 (en) | 2012-12-21 | 2013-12-02 | Steel wire rod for high-strength spring with excellent hydrogen embrittlement resistance and manufacturing process therefor and high-strength spring |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104797729A CN104797729A (en) | 2015-07-22 |
| CN104797729B true CN104797729B (en) | 2018-01-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201380060180.6A Expired - Fee Related CN104797729B (en) | 2012-12-21 | 2013-12-02 | Resistance to hydrogen embrittlement excellent steel wire for high-strength spring material and its manufacture method and high-strength spring |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US9970072B2 (en) |
| EP (1) | EP2937434B1 (en) |
| JP (1) | JP5973903B2 (en) |
| KR (1) | KR101768785B1 (en) |
| CN (1) | CN104797729B (en) |
| MX (1) | MX371408B (en) |
| TW (1) | TWI551693B (en) |
| WO (1) | WO2014097872A1 (en) |
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|---|---|---|---|---|
| US10557388B2 (en) * | 2015-01-26 | 2020-02-11 | Daido Steel Co., Ltd. | Engine exhaust valve for large ship and method for manufacturing the same |
| EP3330399B1 (en) * | 2015-07-27 | 2020-03-25 | Nippon Steel Corporation | Steel for suspension spring and method for manufacturing same |
| WO2017122828A1 (en) * | 2016-01-15 | 2017-07-20 | 株式会社神戸製鋼所 | Rolled material for high-strength spring |
| WO2017122827A1 (en) * | 2016-01-15 | 2017-07-20 | 株式会社神戸製鋼所 | Wire for high-strength spring, and method for producing same |
| CN106048451A (en) * | 2016-07-06 | 2016-10-26 | 安徽红桥金属制造有限公司 | Wear-resistant alloy spring steel and thermal treatment process thereof |
| CN106011634A (en) * | 2016-07-26 | 2016-10-12 | 路望培 | Spring mechanical material and preparation method thereof |
| KR101867689B1 (en) * | 2016-09-01 | 2018-06-15 | 주식회사 포스코 | Steel wire rod having excellent hydrogen embrittlement resistance for high strength spring, and method for manufacturing the same |
| KR101867709B1 (en) * | 2016-12-06 | 2018-06-14 | 주식회사 포스코 | Wire rod and steel wire for spring having excellent corrosion fatigue resistance and method for manufacturing the same |
| KR101940873B1 (en) * | 2016-12-22 | 2019-01-21 | 주식회사 포스코 | Steel wire rod and steel wire having high toughness and method for manufacturing thereof |
| KR20180074008A (en) * | 2016-12-23 | 2018-07-03 | 주식회사 포스코 | Steel wire rod having excellent hydrogen embrittlement resistance for high strength spring, and method for manufacturing the same |
| US11118251B2 (en) * | 2017-06-15 | 2021-09-14 | Nippon Steel Corporation | Rolled wire rod for spring steel |
| CN109972038B (en) * | 2019-04-01 | 2021-07-20 | 宝钢特钢韶关有限公司 | Steel for ultra-deep well drill rod joint and manufacturing method thereof |
| KR102355675B1 (en) * | 2019-07-12 | 2022-01-27 | 주식회사 포스코 | High strength steel wire rod and steel wire for spring and manufacturing method same |
| CN111979388A (en) * | 2020-07-28 | 2020-11-24 | 常州龙腾光热科技股份有限公司 | Manufacturing method of 65Mn spring plate of trough type solar heat collector |
| KR102531464B1 (en) * | 2020-12-18 | 2023-05-12 | 주식회사 포스코 | Steel wire rod, steel wire, and manufacturing method thereof for ultra-high strength springs |
| CN115074627A (en) * | 2022-06-28 | 2022-09-20 | 南京钢铁股份有限公司 | Spring steel belt for tape measure and preparation method thereof |
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- 2013-12-02 EP EP13864637.7A patent/EP2937434B1/en not_active Not-in-force
- 2013-12-02 MX MX2015006912A patent/MX371408B/en active IP Right Grant
- 2013-12-02 CN CN201380060180.6A patent/CN104797729B/en not_active Expired - Fee Related
- 2013-12-02 KR KR1020157015364A patent/KR101768785B1/en active IP Right Grant
- 2013-12-02 WO PCT/JP2013/082380 patent/WO2014097872A1/en active Application Filing
- 2013-12-02 US US14/439,864 patent/US9970072B2/en not_active Expired - Fee Related
- 2013-12-12 TW TW102145881A patent/TWI551693B/en not_active IP Right Cessation
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| CN101365820A (en) * | 2006-01-23 | 2009-02-11 | 株式会社神户制钢所 | High-strength spring steel excellent in brittle fracture resistance and method for producing same |
| CN101484601A (en) * | 2006-05-10 | 2009-07-15 | 住友金属工业株式会社 | Hot-pressed steel sheet member and process for production thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| KR101768785B1 (en) | 2017-08-17 |
| JP5973903B2 (en) | 2016-08-23 |
| EP2937434A4 (en) | 2017-01-04 |
| US20150292052A1 (en) | 2015-10-15 |
| WO2014097872A1 (en) | 2014-06-26 |
| KR20150081366A (en) | 2015-07-13 |
| CN104797729A (en) | 2015-07-22 |
| MX371408B (en) | 2020-01-29 |
| US9970072B2 (en) | 2018-05-15 |
| TW201441382A (en) | 2014-11-01 |
| MX2015006912A (en) | 2015-09-16 |
| EP2937434B1 (en) | 2019-02-20 |
| JP2014122393A (en) | 2014-07-03 |
| TWI551693B (en) | 2016-10-01 |
| EP2937434A1 (en) | 2015-10-28 |
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